Photographic gelatin layers containing the salts of various alkyl and alkenyl succinamates as coating aids



Jersey No. Drawing. Filed Dec. 4, 1961, Ser. No. 156,97 3 Claims. (Cl.9694) v This invention relates to improved gelatin coating compositionscontaining certain -succinamates as coa ting aids and their. applicationto base and paper.

In the photographic industry it is frequently desirable to apply two ormore gelatin layers tofilm base or paper.

This may be conveniently accomplished by successive coating or bymultiple coating as described in U.S. Patent 2,761,791. That patentdiscloses a method 'of applying Unitcd States Patent 0 a plurality ofseparate coatings to the surface of a moving Y 7 web simultaneouslywhile still maintaining a distinct layer relationship between thecoatings after deposition. Essentially, this method involvescontinuously forming each fluid composition into a layer of giventhickness, bringing these layers into surface Contact prior to the timethey are applied to the surface ofthe web and directing them while incombined relation to the point of where they are applied simultaneouslytofthe web in the desired orientatioii with no noticeable mixing-orcontamination at the interface of the layers. Apparatus forthesimultaneous applicationof multiple coatings is described in U.S.Patents 2,761,417 and 2,761,418; The term successive coating referstocoating a gelatin layer on a support and, before that coating has dried,applying. another gelatin layer thereover. This method of coating aplurality of gelatin layers on a support is also referred to aswet-onwet coating. g

Gelatin coatings applied simultaneously in accordance with the methoddescribed .in' the above-identified patent but without the use of acoating aid, are unsatisfactory :in several respects. Crescent-shapeduncoated areas (repellencies) probably attributable to oil impurities inthe gelatin are found in the coating. These defects may be about thesize of a pinhead with streaks running down from the points of thecrescent in a direction opposite to that of the coating. In addition,longitudinal pencil-line streaks and double-edge comets may appear inthe coating. Accordingly, a number of coating aids have been tested,some of which have been found toproduce blemishfree coatings. However;the coatings produced with these coating aids when dried have beengenerally considered unsatisfactory because of surface slickness orinadequate rewettability. Handling problems result from surfaceslickness while inadequate rewettability causes processin difiiculties.

A number of coating aids have beensuggested to facilitatesingle-layergelatin coatings. saponin which; when employed insingle-layer coatings,

'efiectively suppresses repellencies and yields dried coatings withsatisfactory developer wettability and adequate surface roughness.However, in the simultaneous appli:

cation of two or'more gelatin layers to a base or paper,

saponin is ineffective to prevent pencil-line streaks and double-edgedcomets. Saponin is a naturally occurring substance which varies inquality and composition from A notable example is Ice batch to batchwhich may. cause an increasein fog or a change in phot'ographicsensitivity. H ence, various synthetic coating aids have been'propos'edfor single-layer inadequate rewettabilityor defects in the coatingitself, 3

such as pencil-line streaks or double-edged comets.

We have now found a class of compoundswhich may be employed as coatingaids in single-layer gelatin coatings, or simultaneous gelatincoatingoperations to produce blemish-free coatings which, when dried,possess the necessary surface roughness and rewettability. I

One object of our invention is to provide improved gelatincoatingcompositionscontaining certain succinamates as coating aids. Anotherobjectof our invention. is to provide a plurality of coatingcompositions which may be simultaneously applied to a base or paper toproduce substantially blemish-free coatings having adequate surfaceroughness and rewettability. Still other objects of our invention willappear herein.

We have now found that by incorporating certain succinamates as coatingaids in gelatin coating compositions,

improved single-layer coatings areobtained. We have also found thatthese succinamate's may be incorporated into a plurality of gelatincoating compositions which J may be coated successively orsimultaneously onto film base or paper. The succinamates which: we havefound to be useful are indicated in the following formula:

thegroup consisting of alkyl and alkenyl radicals con- (x being 2-5 andy being 1-4, the sum of x and y being 3-9) and--C(CHOH) (CH ),,CH (nbeing 0 to 3),

R where R is selected from the group consisting of CH CH OH and CH CH CHOH, is selected from,

the group consisting of CH CH OH,

- '-CH CH CH OH, -CH (CHOH) CH OH andthe alkyl radicals containing 2 to5 carbon atoms and, M is a salt forming radical such asNa, K, NH

Patented Feb. 16, 196.5

and

, description of i above.

coating aids yl or alkenyl sucin the presence of in protein c'oat thedodecenyl radical is a mixture of branched monoole- V fins formed bytetramerizing propene) with a compound selected from the groupconsisting of 2,2 iminodiethanol;

N-methylglucamine; and l- 2-( 2'-hydroXy) ethOxy-Zeththecoating aidsthusproduced are indicated below.

s ntan .A i

I cannonsoi ronnononnonzon I, on oo'oNa' I and a i i on,

onzoononnononnomon ang, HCOONa uineanoN oH 0H omi on o oio'isra Vongoonionlonzonjz I GXZHM COON Q ou' naorrooNn orig n(001120 95 11ihoniooona ornco is a highly branched monoolefin radical. .-As indicatedabove, various other alkyl and alkenyl substituted sucjcinarnates may beemployed in accordance with this in vention. Representative examplesinclude the followingz' a tetramethylbutylsuccinamic acid, .SOClilIIIlsalt; a V

branchedchain-dodecylsuccinamic acid, sodium salt; a

Branched-chain tridecylsuccinamic acid, sodium salt; a

branched-chain 'p'entadecylsuccinamic acid, sodium salt; a

branched-chainhexadecylsuccinamic acid, sodium salti a branched-chainnonenylsuccinamic acid, sodium salt;

- a branched-chain dodecenylsuccin'amic acid, sodium salt;

a branched-chain pentad'ec'enylsnccinamic. acid, sodium salt;,and,, abranched chain hexadecenylsuccinamic acid,

sodium salt. In each of the foregoing compounds, the alkyl or alkenylradical contains not less thantwo points.

'fof branching. Of-course, the substituents attached to the nitrogenatom in these compounds conform to the general the succinamates of ourinvention given v The coating materials containing our agent may be ofvarious compositions; However, for general explanation, I

reference Will be made to proteinaceous coating compositions of aphotographic nature. Such coatings are illustrated by. gelatincontaining various sensitive components to in somedetail inasmuch as itconcerns our preferred embodiment and also presents'more problems thancertainother coating compositions. That is, whilein the art many kindsof surface-active agents have been added to coating compositions and dofacilitate their, 'coating,never,-"

,theless such agents would not be suitable in compositions such asthephotographic coatings under-description since such agents may injurethe light-sensitive photographic 15. in appears unnecessary.

fit uanooazonna fly The dodecenyl radical of'the above compounds conitains not less than two points Tofbranching, and generally application.Y z

mateiials Hence, "it is thought that sho present, our invention wouldlikewise have utility and A sfju'st mentioned, or a medium such as.

or bromide. The emulsionmay likewise contain dyes 1 and'various othermaterials. Inasmuch as: a description .The structurallformulas of" usualconventional base materials. ticular reference is made to a paper base.A' description rial of this typewould preterahly be usediin the presentinvention.

ofemulsion coatings is found inthe publication Fonda mentals ofPhotographic Theory .by;T. H. James and.

George C. Higgins, published in 3. John W. .Wiley & Sons, Inc, ChapterZ, further detailed description here- The. base, to'be coated composedof ,any :ot the of photographicjpaper is found in Kodak DataBool-z, 5thEdition, Kodak-Papers, pages? and4. A basemate- The over-all coatingprocedures which may be utilized comprise any otfthe standard proceduresemployed in'the 7 industry. Chief amongfthese'. are the extrusion hoppercoatings from which the coating rneltin a single layer coatingis'delivered, at a measured rate, orvarious coating melts in amultilayer coating are. delivered simultaneously,

each at a measured rate, to the support so as to give dried.

:- coatings with layers of the desired. thickness in accordanc-e Withthel jnethod outlined in US. Patent 2,761,791, A withapparatus-disclosed in U.S. Patent 2,761,417, or

2,761,418. r V r In practicing our invention; the coating compositionwhich it is desired to apply to a film base or paperis prepared in theusual manner. However, at sometime before a the actual coatingoperationthereiis' incorporated into the coatingcompositiona surface-active agentof thepresent invention. 'This'incorporatiodmay be accomplished*ad--vantag eouslyinthe following "manner: A 2.5% aqueous solution ot thecoating aid may be prepared; An amount equal to 0.0410 1.0 gram ,(dryweight) of coating aid 7 from a consideration of the severalspecifieexamples which'follow. In these examples a single pelloid coating wasapplied to-a film base, using the preferre'd coating aids per 454 g.oficoating solution'fis added to'thegelatin- .silver'halide emulsion atany point after the emulsionis in a liquid state, either.before,"during,o ft th lion Of other materials; 1

f A further understanding ot our invention will be had referred to aboveat a concentration of 0.22 gram per "such as silver salts. This type ofcomposition is referred I j number of uncoated spots. 1 lar coatingexperiment in 454 g. of wet coating melt, The resultsare shown in thefollowing t'able: v V I Table I 7 p Repellenoies Longitudinal Surfactanton 25 sq. ft. Mottle" .Streaks 'ofQoating, a o VerySllghtr 0' D0. (l.Do.

21- SlightJ 1 In the abovetable, by RepellenciesTiye referto the TheControl involved a sirni which no, surfactant'was used;

.A series of experiments were conducted in which a' gelatinrsilver.halide photographic emulsion and, its clear gelatin overcoat wereappliedsimultaneously to a paper support using a hopper technique andcoating aids in accordance with our invention in each layer. The resultsare 'shownin thefollowing table:

vving that the present invention functions an environment of lighthsensitive photographic,coatings, it will be apparent 7 that even Wherethe problem of photographicsensitivityis not photographic'coatings arecomprised V gelatin which contains light-sensitive v material comprisinga silver salt such as jsilverlchloride In this. invention par- I 53Table II Concentration of Surfactant, g.

Developer Coeflficient Repel- Surfactant Spread, lencies Per 454 g. Per454 g. .cm. Friction 2 Emulsion Clear Gelatin 0.13 g 0. 5 8. 55 0.497None. 0. 25 0. 5 12. G 0. 497 D0. 0. 0. 5 15. 90- 0. 497 Do. 0. 13 0. 5r 6. 60' 0. 408 None. 0.25 0.5 13. 90 0. 442 D0. 0.5 0.5 4). 08 0. 408Do. 0.13 0. 5 8.04 0. 276 None 0.25 0.5 9.08 0.276 Do. 0.5 0.5 11. 900.276 Do.

One cc. of developer solution is deliveredto a surface of a papersupport coated with a photographic emulsion and a clear gelatin coatthereover, and the area which develops in about 30 seconds was measured.This test indicates how effectively an emulsion containing a coating aidof our invention will wet. A developer spread of 4.0 cm. or more isdesirable.

2 Two sheets of a paper support were coated with a gelatin-silver halidephotographic emulsion and a clear gelatin coating thereover, and onesheet was placed upon the other so that the uncoated side of one papersupport was against the coated side of the other paper support.- Thecoeflicient of friction was measured to determine the sliclrness ofgelatin coatings containing the coating aids of this invention.Difliculties occur instacking coated sheets when the coet'dcient offriction is less than about .25.

, 3 The number of uncoated spots on 7.5 sq. ft. of coating.

The occurrence of pencil-line streaks is a persistent defeet in coatingsachieved by the simultaneous application of two gelatin layers to a filmbase or paper. The ability of a coating aid to reduce the incidence ofpencil-line in different concentrations, to determine their ability tocontrol pencil-line streaks in simultaneously applied gelatin coatings.The results are shown in Table III.

Table III Surfactant Surfactant Concentration, Saponin grams per poundill HO one of R and R being H, the other being selected from the groupconsisting of the alkyl and the alkenyl radicals containing 8-16 carbonatomshaving at least two points of branching; R is selected from thegroup consisting of --H, CH --CH CH OH and -CH CH CH O-H; R where R isselected from the group consisting of H 6 and -CH is selected from theCH (CHOH) .zCHzOH; U

(x beings-s, y being 1-4,.the"sum-of x and y-being. 3-9 and --C(CH OH)(CH CH n being"0-3);'

. 2. A photographic element comprisin'g a flexible photographic base, alight-sensitive coating thereon containing a gelatin silver halideemulsion, and a clear gelatin coating thereover, at least one of thelatter two coatings containing as a coating aid a compound having thefolone of R and R being H, the other being selected from the groupconsisting of the alkyl and the .alkenyl radicals containing 8-16 carbonatoms having at least two points of branching R is selected from thegroup consisting of H, -CH3, and R where R is selected from the groupconsisting of H and -CH is selected from the group consisting of --CH(CHOH) CH OH,

(x being 2-5, y being 1-4, the sum of x and ybeing 3-9 and -C(CH2OI-I)2(CH2),1C,H3' (n being 0 3 R4, where R3 is selected from the groupconsisting'of -CH CH OH and CH CH CH O-H, is selected from",

the group consisting of CH CH OH,

CH (CHOH) CH OH and the alkyl'radicals containing 2 to 5 carbon atoms;and, M is a salt forming sub stituten't, which coating aid provides fthephotographic element with good surface roughness to prevent slippagewhen sheets of the photographic element are stacked upon one another,and imparts good rewettability characteristics to facilitate developmentof the photographic element. 1

.3. A gelatin-silver halide emulsion containing as a coating aid acompound having the following formula:

H 0 R, R1( 3- I T R4 m- O0M I I I one of R and R being H, the otherbeing selected from the group consisting of the alkyl and the alkenylradicals containing 8-16 carbon atoms having at least two points ofbranching; R is selected from the group consisting R where R is selectedfrom the group consisting of H and -CH is selected from the groupconsisting of CH (CHOH) CH OH,

(x being 2-5, y being 1-4, the sum of x and y being group consisting of

3. A GELATIN-SILVER HALIDE EMULSION CONTAINING AS A COATING AID ACOMPOUND HAVING THE FOLLOWING FORMULA: